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Synthesis of alkyl cyclopentadiene compounds

a technology of cyclopentadiene and compound, which is applied in the field of olefin polymerization catalysts, can solve the problems of difficult separation of desired cyclopentadienyl compound from aluminum containing byproducts, undesirable levels of impurities, and low yield of desired produ

Active Publication Date: 2015-03-10
UNIVATION TECH LLC
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Benefits of technology

[0092]Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. While compositions and methods are described in terms of “comprising,”“containing,”“having,” or “including” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps.

Problems solved by technology

This technique may be problematic, however, in that it may be difficult to separate the desired cyclopentadienyl compound from the aluminum containing byproducts.
However, the yield and subsequent purity of the product are highly dependent upon reaction conditions.
For example, sodium cyclopentadienide in tetrahydrofuran (“THF”) can react readily with alkyl bromides at room temperature, but the reaction typically results in undesirable levels of impurities and yields of the desired product can be low.
However, despite higher yields, these additional techniques require the use of liquid ammonia at low temperature and the use of alkyl trifluoromethanesulfonates which are expensive, air and moisture sensitive, toxic and may not be readily available.
However, drawbacks from this procedure include, higher levels of impurities from the aqueous work-up.

Method used

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Examples

Experimental program
Comparison scheme
Effect test

example 1

Synthesis of CpC5H11

[0047]To a stirring solution of CpMgCl (50.0 ml, 1.00 M / THF, 50.0 mmol) was added 1-iodopentane (8.4 g, 42 mmol). The solution was heated at 60° C. for a several minutes. After removing it from the heat, the solution continued to boil gently for about 5 minutes. Next, the solution was stirred for 3 hours at room temperature and then heated to 60° C. for 1 hour. The THF was removed from the solution under vacuum, and the resulting material was extracted with pentane (60 ml) with the liquid extract isolated by filtration. The isolated liquid was transferred to a new flask. The remaining solid was washed with pentane (20 ml) and filtered. The isolated liquid from the pentane extraction and the liquid from the wash were combined and placed under vacuum to remove the pentane and yield the product, a light yellow liquid. Yield=4.0 grams (69% based on 1-iodopentane).

[0048]1H NMR Spectra were obtained for the alkyl cyclopentadiene compounds prepared in this example. 1H ...

example 2

Synthesis of CpC6H13

[0049]Sample 1. To a stirring solution of CpMgCl (100 ml, 1.1 M / THF, 110 mmol) was added 1-bromohexane (13.6 g, 82.4 mmol). The solution was heated at 60° C. for 4.5 hours. THF was then removed under vacuum, and the resulting material was extracted with pentane (100 ml) with the liquid extract isolated by filtration. The isolated liquid was transferred to a new flask. The remaining solid was washed with pentane (30 ml) and filtered. The isolated liquid from the pentane extraction and the liquid from the wash were combined and placed under vacuum (1.5 hours) to remove the pentane and yield the product. Yield=8.11 g (65.5% based on 1-bromohexane).

[0050]Sample 2. To a stirring solution of CpMgCl (170 ml, 1.30 M / THF, 221 mmol) was added 1-bromohexane (27.2 g, 165 mmol). The solution was heated at 60° C. for 5 hours. The THF was then removed under vacuum, and the resulting material was extracted with pentane (200 ml) with the liquid extract isolated by filtration. Th...

example 3

Synthesis of CpC7H15

[0053]To a stirring solution of CpMgCl (50.0 ml, 1.00 M / THF, 50.0 mmol) was added 1-bromoheptane (6.72 g, 37.5 mmol). The solution was heated at 60° C. for 9 hours. The THF was then removed under vacuum, and the resulting material was extracted with pentane (40 ml) with the liquid extract isolated by filtration. The isolated liquid was transferred to a new flask. The isolated liquid was placed under vacuum for 1 hour to remove the pentane and yield the product. Yield=4.22 g (68.6% based on 1-bromoheptane).

[0054]1H NMR Spectra were obtained for the alkyl cyclopentadiene compounds prepared in this example. 1H NMR δ 6.47 (m, 2.02H), 6.35 (m, 1.12H), 6.22 (m, 0.94H), 6.18 (m, 0.92H), 5.97 (m, 1.15H), 2.79 (m, 2.65H), 2.69 (m, 2.00H), 2.33-2.28 (m, 4.69H), 1.53 (m, 3.04H), 1.46 (m, 2.59H), 1.23 (m, 23.26H), 0.878 (m, 9.0H).

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Abstract

A method of synthesizing an alkyl cyclopentadiene compound is disclosed. The method includes contacting at least one cyclopentadienyl anion source and at least one alkyl group source to form at least one alkyl cyclopentadiene compound. The method further includes extracting the alkyl cyclopentadiene compound with a hydrocarbon solvent. The alkyl cyclopentadiene compound may be converted to a metallocene catalyst compound.

Description

BACKGROUND[0001]Metallocene catalyst compounds are well known olefin polymerization catalysts. While a variety of different techniques may be used to synthesize suitable metallocene catalyst compounds, one technique involves the use of alkyl cyclopentadiene compounds, such as n-propylcyclopentadiene and n-butylcyclopentadiene. Unbridged metallocene catalyst compounds containing at least one n-alkyl cyclopentadienyl ligand (propyl or longer) can show increased productivity over metallocene catalyst compounds that do not contain this group. This increase in productivity has been referred to as the “propyl effect.”[0002]One technique for synthesizing n-alkyl cyclopentadienes involves a fulvene intermediate. The fulvene intermediate may be reduced, for example, with LiAlH4 to produced substituted cyclopentadienide which can then be used directly in the synthesis of the metallocene catalyst compound. This technique may be problematic, however, in that it may be difficult to separate the ...

Claims

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Application Information

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Patent Type & Authority Patents(United States)
IPC IPC(8): C07F17/00B01J31/22C07C2/54C07C17/32C07C1/32C07C2/86C07C41/30
CPCC07C2/54C07C1/326C07C2/861C07C2/868C07F17/00B01J31/2295C07C17/32C07C41/30C07C13/15C07C2101/10C07C2601/10
Inventor HARLAN, C. JEFFCAO, XIANYIRIX, FRANCIS C.
Owner UNIVATION TECH LLC